CHAPTER 5: Non-Reactive Gas Mixtures

AVOGADRO’S LAW
A mole of a substance has a mass numerically equal to the molecular weight of the substance. One g
mol of oxygen has a mass of 32 gm, 1 kmol of oxygen has a mass of 32 kg, 1 kmol of nitrogen has a
mass of 28 kg, and so on.
Avogadro’s law states that:
the volume of a g mol of all gases at the pressure of 760 mm Hg and temperature of 0°C is the
same, and is equal to 22.4 litres.
Therefore, 1 g mol of a gas has a volume of 22.4 × 103 cm3 (22.4 litre) and 1 kmol of a gas has a
volume of 22.4 m3 at normal temperature and pressure (N.T.P.).

For a certain gas, if m is its mass in kg, and M its molecular weight, then the number of kmoles of the
gas, n, would be given by
𝑚 (𝑘𝑔) 𝑚
𝑛= = 𝑘𝑚𝑜𝑙𝑒𝑠
𝑀 (𝑘𝑔/𝑘𝑚𝑜𝑙) 𝑀
The molar volume, 𝑣 , is given by
𝑉 𝑉 𝑣
𝑣 = 𝑚3 /𝑘𝑚𝑜𝑙 𝑎𝑛𝑑 𝑣 = = 𝑚3 /𝑘𝑔
𝑛 𝑚 𝑀
where V is the total volume of the gas in m3.

EQUATION OF STATE OF A GAS

The functional relationship among the properties, pressure p, molar or specific volume v, and
temperature T, is known as an equation of state, which may be expressed in the form,
𝑓 ( 𝑝, 𝑣, 𝑇 ) = 0
If two of these properties of a gas are known, the third can be evaluated from the equation of state.
IDEAL GAS: A hypothetical gas which obeys the law 𝑝𝑣 = 𝑅𝑇 or 𝑝𝑣 = 𝑅𝑇 at all pressures and
temperatures is called an ideal gas. Real gases do not conform to this equation of state with complete
accuracy.

As 𝑝 → 0, or 𝑇 → ∞, (i.e. at very low pressures and very high temperatures) the real gas approaches
the ideal gas behaviour.

In the equation 𝑝𝑣 = 𝑅𝑇, as 𝑇 → 0, i.e. 𝑡 → −273.15°𝐶

if 𝑣 remains constant, 𝑝 → 0,
or if p remains constant 𝑣 → 0.
Since negative volume or negative pressure is inconceivable, the lowest possible temperature is 0 K or
- 273.15°C. T is, therefore, known as the absolute temperature.

There is no permanent or perfect gas. At atmospheric condition only, these gases exist in the gaseous
state. They are subject to liquefication or solidification, as the temperature and pressure are sufficiently
lowered.
From Avogadro’s law, when p = 760 mm Hg = 1.013 × 105 N/m2, T = 273.15 K, and 𝑣 = 22.4 m3/kmol
1.013 × 105 × 22.4 𝑁𝑚
𝑅= = 8314.3 = 8.3143 𝑘𝐽/𝑘𝑚𝑜𝑙. 𝐾
273.15 𝑘𝑚𝑜𝑙. 𝐾
Since 𝑣 = 𝑉/𝑛, where V is the total volume and n the number of moles of the gas, the equation of
state for an ideal gas may be written as
𝑚𝑅𝑇
𝑝𝑣 = 𝑅𝑇 → 𝑝𝑉 = 𝑛𝑅𝑇 = = 𝑚𝑅𝑇
𝑀
Where,
𝑅
𝑅 = 𝑐ℎ𝑎𝑟𝑎𝑐𝑡𝑒𝑟𝑖𝑠𝑡𝑖𝑐𝑠 𝑔𝑎𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑟 =
𝑀
For oxygen, e.g
8.3143
𝑅𝑂2 = = 0.262 𝑘𝐽/𝑘𝑔. 𝐾
32
For air,
8.3143
𝑅𝑎𝑖𝑟 = = 0.287 𝑘𝐽/𝑘𝑔. 𝐾
28.96
There are 6.023 × 1023 molecules in a g mol of a substance. This is known as Avogadro’s number (A).
𝐴 = 6.023 × 1026 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠/𝑘𝑚𝑜𝑙
In n kmoles of gas, the total number of molecules, N, are
𝑁 = 𝑛𝐴 → 𝑛 = 𝑁/𝐴
Therefore,
𝑅
𝑝𝑉 = 𝑛𝑅𝑇 = 𝑁 𝑇 = 𝑁𝐾𝑇;
𝐴
𝑅 8314.3
𝑤ℎ𝑒𝑟𝑒, 𝐾 = 𝐵𝑜𝑙𝑡𝑧𝑚𝑎𝑛𝑛 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = = = 1.38 × 10−23 𝐽/𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒. 𝐾
𝐴 6.023 × 1026
Therefore, the equation of state of an ideal gas is given by
𝑝𝑉 = 𝑚𝑅𝑇 = 𝑛𝑅𝑇 = 𝑁𝐾𝑇

Specific Heats, Internal Energy, and Enthalpy of an Ideal Gas

An ideal gas not only satisfies the equation of state 𝑝𝑣 = 𝑅𝑇, but its specific heats (𝑐𝑝 𝑎𝑛𝑑 𝑐𝑣 ) are
constant also. For real gases, the specific heats (𝑐𝑝 𝑎𝑛𝑑 𝑐𝑣 ) vary appreciably with temperature, and
little with pressure.

The properties of a substance are related by: (theses equations have been derived in the previous
chapter)
𝑇𝑑𝑆 = 𝑑𝑈 + 𝑝𝑑𝑉
𝜕𝑝
𝑑𝑈 = 𝐶𝑣 𝑑𝑇 + [𝑇 ( ) − 𝑝] 𝑑𝑉
𝜕𝑇 𝑉
𝜕𝑈 𝜕𝑝
( ) = 𝑇( ) −𝑝
𝜕𝑉 𝑇 𝜕𝑇 𝑉
For an ideal gas,
𝜕𝑈 𝜕𝑝
( ) = 𝑇 ( ) − 𝑝 = 0 𝑎𝑛𝑑 𝑑𝑈 = 𝐶𝑣 𝑑𝑇, 𝑜𝑟, 𝑑𝑢 = 𝑐𝑣 𝑑𝑇
𝜕𝑉 𝑇 𝜕𝑇 𝑉
𝑇𝑑𝑆 = 𝑑𝐻 − 𝑉𝑑𝑝
 𝜕𝑉
𝑑𝐻 = 𝐶𝑝 𝑑𝑇 + [𝑉 − 𝑇 ( ) ] 𝑑𝑝
𝜕𝑇 𝑝

𝜕𝐻 𝜕𝑉
( ) = 𝑉 −𝑇( )
𝜕𝑝 𝑇 𝜕𝑇 𝑝

For an ideal gas,

𝜕𝐻 𝜕𝑉
( ) = 𝑉 − 𝑇 ( ) = 0 𝑎𝑛𝑑 𝑑𝐻 = 𝐶𝑝 𝑑𝑇, 𝑜𝑟, 𝑑ℎ = 𝑐𝑝 𝑑𝑇
𝜕𝑝 𝑇 𝜕𝑇 𝑝

For an ideal gas, enthalpy and internal energy are functions of temperature only.
Specific heats for an ideal gas are related by:
𝑐𝑝
𝑐𝑝 − 𝑐𝑣 = 𝑅 𝑎𝑛𝑑 =𝛾
𝑐𝑣

𝑐𝑝 , and 𝑐𝑣 are specific heats at constant pressure and at constant volume, respectively.

Therefore,
𝛾𝑅 𝑅 𝑘𝐽
𝑐𝑝 = 𝑎𝑛𝑑 𝑐𝑣 =
𝛾−1 𝛾 − 1 𝑘𝑔. 𝐾
Also,
𝑅 𝛾𝑅 𝑘𝐽
𝑐𝑣 = 𝑀𝑐𝑣 = 𝑎𝑛𝑑 𝑐𝑝 = 𝑀𝑐𝑝 =
𝛾−1 𝛾 − 1 𝑘𝑚𝑜𝑙. 𝐾
𝑐𝑣 and 𝑐𝑝 are molar or molal specific heats at constant volume and at constant pressure, respectively.

It can be shown by the classical kinetic theory of gases that the values of  are 5/3 for monatomic gases
and 7/5 for diatomic gases. When the gas molecule contains more than two atoms (i.e. for polyatomic
gases) the value of  may be taken approximately as 4/3. Thus, the minimum value of  is 1 and the
maximum is 1.67.
The value of  thus depends only on the molecular structure of the gas, i.e. whether the gas is
monatomic, diatomic or polyatomic having one, two or more atoms in a molecule.
𝑅
It may be noted that 𝑐𝑝 and 𝑐𝑣 of an ideal gas depend only on  and R (= ), i.e. the number of atoms
𝑀
in a molecule and the molecular weight of the gas. They are independent of temperature or pressure of
the gas.

Entropy Change of an Ideal Gas

From the general property relations
𝑇𝑑𝑠 = 𝑑𝑢 + 𝑝𝑑𝑣 and 𝑇𝑑𝑠 = 𝑑ℎ − 𝑣𝑑𝑝

and for an ideal gas,

𝑑𝑢 = 𝑐𝑣 𝑑𝑇, 𝑑ℎ = 𝑐𝑝 𝑑𝑇 𝑎𝑛𝑑 𝑝𝑣 = 𝑅𝑇,
the entropy change between any two states 1 and 2 may be computed as given below
𝑐𝑣 𝑑𝑇 𝑝 𝑐𝑣 𝑑𝑇 𝑅
𝑑𝑠 = + 𝑑𝑣 = + 𝑑𝑣
𝑇 𝑇 𝑇 𝑣
Therefore,
𝑇2 𝑣2
𝑠2 − 𝑠1 = 𝑐𝑣 𝑙𝑛 ( ) + 𝑅𝑙𝑛 ( ) (1)
𝑇1 𝑣1
Also,
𝑐𝑝 𝑑𝑇 𝑣 𝑐𝑝 𝑑𝑇 𝑅
𝑑𝑠 = − 𝑑𝑝 = − 𝑑𝑝
𝑇 𝑇 𝑇 𝑝
Integrating,
𝑇2 𝑝2
𝑠2 − 𝑠1 = 𝑐𝑝 𝑙𝑛 ( ) − 𝑅𝑙𝑛 ( ) (2)
𝑇1 𝑝1
Since, 𝑐𝑝 − 𝑐𝑣 = 𝑅,
𝑇2 𝑝2 𝑝2
𝑠2 − 𝑠1 = 𝑐𝑝 𝑙𝑛 ( ) − 𝑐𝑝 𝑙𝑛 ( ) + 𝑐𝑣 𝑙𝑛 ( )
𝑇1 𝑝1 𝑝1

𝑇2 𝑝1 𝑝2 𝑣2 𝑝2
→ 𝑠2 − 𝑠1 = 𝑐𝑝 𝑙𝑛 ( × ) + 𝑐𝑣 𝑙𝑛 ( ) = 𝑐𝑝 𝑙𝑛 ( ) + 𝑐𝑣 𝑙𝑛 ( ) (3)
𝑇1 𝑝2 𝑝1 𝑣1 𝑝1

Any one of the three equations may be used for computing the entropy change between any two states
of an ideal gas.

Reversible Adiabatic Process

The general property relations for an ideal gas may be written as
𝑇𝑑𝑠 = 𝑑𝑢 + 𝑝𝑑𝑣 = 𝑐𝑣 𝑑𝑇 + 𝑝𝑑𝑣
and

𝑇𝑑𝑠 = 𝑑ℎ − 𝑣𝑑𝑝 = 𝑐𝑝 𝑑𝑇 − 𝑣𝑑𝑝

For a reversible adiabatic change, ds = 0, therefore,

𝑐𝑝 𝑑𝑇 = 𝑣𝑑𝑝 𝑎𝑛𝑑 𝑐𝑣 𝑑𝑇 = −𝑝𝑑𝑣
By division,
𝑐𝑝 𝑣𝑑𝑝 𝑑𝑝 𝑑𝑣
=𝛾=− → +𝛾 =0 → 𝑑(𝑙𝑛𝑝) + 𝛾𝑑(𝑙𝑛𝑣) = 𝑑(𝑙𝑛𝑐)
𝑐𝑣 𝑝𝑑𝑣 𝑝 𝑣

Where, c is a constant. Therefore,

(𝑙𝑛𝑝) + 𝛾(𝑙𝑛𝑣) = (𝑙𝑛𝑐) → 𝑝𝑣 𝛾 = 𝑐
Between two states 1 and 2,
𝑝2 𝑣1 𝛾
𝑝1 𝑣1 𝛾 = 𝑝2 𝑣2 𝛾 → =( )
𝑝1 𝑣2
For an ideal gas,
𝑝𝑣 = 𝑅𝑇 → 𝑐𝑣 −𝛾 . 𝑣 = 𝑅𝑇 → 𝑇𝑣 𝛾−1 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

Between two states 1 and 2, for a reversible adiabatic process in the case of an ideal gas
𝑇2 𝑣1 𝛾−1
𝑇1 𝑣1 𝛾−1 = 𝑇2 𝑣2 𝛾−1 → =( )
𝑇1 𝑣2
Similarly,
𝑐 1⁄𝛾 𝑐′
𝑝𝑣 𝛾 = 𝑐 → 𝑣 = ( ) = 1⁄𝛾
𝑝 𝑝
′
𝑐
𝑝𝑣 = 𝑅𝑇 → 𝑝. 1⁄𝛾 = 𝑅𝑇 → 𝑇𝑝(1⁄𝛾)−1 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑝
→ 𝑇𝑝(1−𝛾)⁄𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
Between two states 1 and 2,
𝑇2 𝑝1 (1−𝛾)⁄𝛾 𝑝2 (𝛾−1)⁄𝛾
𝑇1 𝑝1 (1−𝛾)⁄𝛾 = 𝑇2 𝑝2 (1−𝛾)⁄𝛾 → =( ) =( )
𝑇1 𝑝2 𝑝1
𝑇2 𝑝2 (𝛾−1)⁄𝛾 𝑣1 𝛾−1
=( ) =( )
𝑇1 𝑝1 𝑣2
The above equations give the relations among p, v, and T in a reversible adiabatic process for an ideal
gas.
The internal energy change of an ideal gas for a reversible adiabatic process is given by
2 2 2
𝑇𝑑𝑠 = 𝑑𝑢 + 𝑝𝑑𝑣 = 0 → ∫ 𝑑𝑢 = − ∫ 𝑝𝑑𝑣 = − ∫ 𝑐𝑣 −𝛾 𝑑𝑣
1 1 1
Where,
𝑐 = 𝑝𝑣 𝛾 = 𝑝1 𝑣1 𝛾 = 𝑝2 𝑣2 𝛾

1−𝛾 1−𝛾 1−𝛾 1−𝛾

𝑣2− 𝑣1 𝑝2 𝑣2 𝛾 . 𝑣2 − 𝑝1 𝑣1 𝛾 . 𝑣1 𝑝2 𝑣2 − 𝑝1 𝑣1 𝑅(𝑇2 − 𝑇1 )
→ 𝑢2 − 𝑢1 = 𝑐 = = =
𝛾−1 𝛾−1 𝛾−1 𝛾−1
𝑅𝑇1 𝑇2 𝑅𝑇1 𝑝2 𝛾−1 ⁄ 𝛾
= ( − 1) = [( ) − 1]
𝛾 − 1 𝑇1 𝛾 − 1 𝑝1

The enthalpy change of an ideal gas for a reversible adiabatic process may be similarly derived.
𝑅(𝑇2 − 𝑇1 ) 𝛾𝑅(𝑇2 − 𝑇1 )
ℎ2 − ℎ1 = 𝑢2 − 𝑢1 + 𝑝2 𝑣2 − 𝑝1 𝑣1 = + 𝑅(𝑇2 − 𝑇1 ) =
𝛾−1 𝛾−1
𝛾𝑅𝑇1 𝑝2 𝛾−1 ⁄𝛾
= [( ) − 1]
𝛾 − 1 𝑝1
Alternatively, for an ideal gas,
𝑅(𝑇2 − 𝑇1 )
𝑑𝑢 = 𝑐𝑣 𝑑𝑇 → 𝑢2 − 𝑢1 = 𝑐𝑣 (𝑇2 − 𝑇1 ) =
𝛾−1
𝛾𝑅(𝑇2 − 𝑇1 )
𝑑ℎ = 𝑐𝑝 𝑑𝑇 → ℎ2 − ℎ1 = 𝑐𝑝 (𝑇2 − 𝑇1 ) =
𝛾−1
The work done by an ideal gas in a reversible adiabatic process is given by
𝛿𝑄 = 𝑑𝑈 + 𝛿𝑊 → 𝛿𝑊 = −𝑑𝑈
i.e. work is done at the expense of the internal energy. Thus,
𝑚(𝑝1 𝑣1 − 𝑝2 𝑣2 ) 𝑚𝑅(𝑇1 − 𝑇2 )
𝑊1−2 = 𝑈1 − 𝑈2 = 𝑚(𝑢1 − 𝑢2 ) = =
𝛾−1 𝛾−1
𝑅𝑇1 𝑇2 𝑚𝑅𝑇1 𝑝2 𝛾−1 ⁄𝛾
= (1 − ) = [1 − ( ) ]
𝛾−1 𝑇1 𝛾−1 𝑝1
where m is the mass of gas.

In a reversible adiabatic steady flow process, where both flow work and external work are involved,
we have from S.F.E.E.,
𝑉22 − 𝑉12 𝛾𝑅(𝑇1 − 𝑇2 )
𝑤1−2 + + 𝑔(𝑧2 − 𝑧1 ) = 𝑞1−2 + ℎ1 − ℎ2 = 𝑐𝑝 (𝑇1 − 𝑇2 ) = =
2 𝛾−1
𝛾(𝑝1 𝑣1 − 𝑝2 𝑣2 ) 𝛾𝑝1 𝑣1 𝑝2 𝛾−1⁄𝛾
= = [1 − ( ) ]
𝛾−1 𝛾−1 𝑝1
If K.E. and P.E. changes are neglected,
𝛾𝑝1 𝑣1 𝑝2 𝛾−1⁄𝛾
𝑤1−2 = ℎ1 − ℎ2 = [1 − ( ) ]
𝛾−1 𝑝1

Reversible Isothermal Process

When an ideal gas of mass m undergoes a reversible isothermal process from state 1 to state 2,
𝑑𝑢 = 𝑐𝑣 𝑑𝑇 = 0 𝑎𝑛𝑑 𝑑ℎ = 𝑐𝑝 𝑑𝑇 = 0
𝛿𝑄 = 𝑑𝑈 + 𝛿𝑊 → 𝛿𝑊 = 𝛿𝑄
the work done is given by
2 2 𝑉2
𝑚𝑅𝑇
∫ 𝛿𝑊 = ∫ 𝑝𝑑𝑉 = ∫ 𝑑𝑉
1 1 𝑉1 𝑉
𝑉2 𝑝1
→ 𝑊1−2 = 𝑚𝑅𝑇𝑙𝑛 ( ) = 𝑚𝑅𝑇𝑙𝑛 ( )
𝑉1 𝑝2
The heat transfer involved in the process
𝑉2
𝑄1−2 = 𝑈2 − 𝑈1 + 𝑊1−2 = 𝑊1−2 = 𝑚𝑅𝑇𝑙𝑛 ( ) = 𝑇(𝑆2 − 𝑆1 )
𝑉1
In a reversible isothermal steady flow process
𝑉22 − 𝑉12
𝑤1−2 + + 𝑔(𝑧2 − 𝑧1 ) = 𝑞1−2 + ℎ1 − ℎ2 = 𝑞1−2
2
2 2 𝑝2
𝑚𝑅𝑇
∫ 𝛿𝑊 = ∫ −𝑉𝑑𝑝 = − ∫ 𝑑𝑝
1 1 𝑝1 𝑝
𝑝1 𝑉2
→ 𝑊1−2 = 𝑚𝑅𝑇𝑙𝑛 ( ) = 𝑚𝑅𝑇𝑙𝑛 ( )
𝑝2 𝑉1

Polytropic Process
An equation of the form 𝑝𝑣 𝑛 = 𝑐, where n is a constant can be used approximately to describe many
processes which occur in practice. Such a process is called a polytropic process.
It is not adiabatic, but it can be reversible.
It may be noted that  is a property of the gas, whereas n is not.
The value of n depends upon the process. It is possible to find the value of n which more or less fits
the experimental results. For two states on the process,
𝑛 𝑛 𝑛
𝑝2 𝑣1 𝑛
𝑝𝑣 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 → 𝑝1 𝑣1 = 𝑝2 𝑣2 → =( )
𝑝1 𝑣2
𝑛−1 𝑛−1 𝑛−1
𝑇2 𝑣1 𝑛−1
𝑇𝑣 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 → 𝑇1 𝑣1 = 𝑇2 𝑣2 → =( )
𝑇1 𝑣2
𝑇2 𝑝2 𝑛−1⁄𝑛
𝑇𝑝(1−𝑛)⁄𝑛 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 → 𝑇1 𝑝1 (1−𝑛)⁄𝑛 = 𝑇2 𝑝2 (1−𝑛)⁄𝑛 → = ( )
𝑇1 𝑝1
𝑇2 𝑝2 𝑛−1 ⁄𝑛 𝑣1 𝑛−1 𝑣2 −(𝑛−1)
=( ) =( ) =( )
𝑇1 𝑝1 𝑣2 𝑣1

(i) Entropy Change in a Polytropic Process: In a reversible adiabatic process, the entropy remains
constant. But in a reversible polytropic process, the entropy changes. We have three expressions for
entropy change as given below:
 𝑇2 𝑣2
𝑠2 − 𝑠1 = 𝑐𝑣 𝑙𝑛 ( ) + 𝑅𝑙𝑛 ( )
𝑇1 𝑣1
𝑅 𝑇2 𝑅 𝑇2 (𝑛 − 𝛾)𝑅 𝑇2
= 𝑙𝑛 ( ) − 𝑙𝑛 ( ) = 𝑙𝑛 ( )
𝛾−1 𝑇1 𝑛−1 𝑇1 (𝛾 − 1)(𝑛 − 1) 𝑇1

Relations in terms of pressure and specific volume can be similarly derived. These are

𝑛−𝛾 𝑝2
𝑠2 − 𝑠1 = 𝑅𝑙𝑛 ( )
𝑛(𝛾 − 1) 𝑝1

𝑛−𝛾 𝑣2
𝑠2 − 𝑠1 = − 𝑅𝑙𝑛 ( )
(𝛾 − 1) 𝑣1

It can be noted that when n = , the entropy change becomes zero.

If p2 > p1,
for n < , the entropy of the gas decreases, and
for n > , the entropy of the gas increases.
The increase of entropy may result from reversible heat transfer to the system from the surroundings.
Entropy decrease is also possible if the gas is cooled.

(ii) Heat and Work in a Polytropic Process:

(a) For a closed system: Using the first law to unit mass of an ideal gas,
𝑚𝑅(𝑇2 − 𝑇1 ) 𝑝2 𝑉2 − 𝑝1 𝑉1
𝑄1−2 − 𝑊1−2 = 𝑈2 − 𝑈1 = 𝑚𝑐𝑣 (𝑇2 − 𝑇1 ) = =
𝛾−1 𝛾−1
𝑚𝑅𝑇1 𝑇2 𝑚𝑅𝑇1 𝑝2 𝑛−1⁄𝑛
𝑄1−2 − 𝑊1−2 = ( − 1) = [( ) − 1]
𝛾 − 1 𝑇1 𝛾 − 1 𝑝1
In general, both heat and work are involved in a polytropic process. To evaluate the heat
transfer during such a process, it is necessary to first evaluate the work via

For a closed system:

2 2
𝑊1−2 = ∫ 𝛿𝑊 = ∫ 𝑝𝑑𝑉
1 1

(b) For an open system: For a steady flow system of unit mass of ideal gas, the S.F.E.E. Eq. gives
𝑉22 − 𝑉12
𝑞1−2 − 𝑤1−2 − − 𝑔(𝑧2 − 𝑧1 ) = ℎ2 − ℎ1 = 𝑐𝑝 (𝑇2 − 𝑇1 )
2
𝛾𝑅(𝑇2 − 𝑇1 ) 𝛾(𝑝2 𝑣2 − 𝑝1 𝑣1 ) 𝛾𝑝1 𝑣1 𝑝2 𝑛−1⁄𝑛
= = = [( ) − 1]
𝛾−1 𝛾−1 𝛾 − 1 𝑝1

Work transfer for an open steady flow system

2 2
𝑤1−2 = ∫ 𝛿𝑤 = ∫ −𝑣𝑑𝑝
1 1
The application of the first law will then yield the heat transfer.
The polytropic processes for various values of n are shown in the following Figure on the p-v and T-s
diagrams.

On differentiating, 𝑝𝑣 𝑛 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑑𝑝 𝑝
𝑣 𝑛 𝑑𝑝 + 𝑝𝑛𝑣 𝑛−1 𝑑𝑣 = 0 → = −𝑛
𝑑𝑣 𝑣
The slope of the curve increases in the negative direction with increase of n. The values of n for some
familiar processes are given below
Isobaric process ( p = c), n = 0
Isothermal process (T = c), n = 1
Isentropic process (s = c), n = 
Isometric or isochoric process (v = c), n  .

EQUATIONS OF STATE
The ideal gas equation of state pv = RT can be established from the postulates of the kinetic
theory of gases developed by Clerk Maxwell, with two important assumptions –
(i) there is little or no attraction between the molecules of the gas, and

(ii) that the volume occupied by the molecules themselves is negligibly small compared to the
volume of the gas.

When pressure is very small or temperature very large, the intermolecular attraction and the
volume of the molecules compared to the total volume of the gas are not of much significance, and the
real gas obeys very closely the ideal gas equation.
But as pressure increases, the intermolecular forces of attraction and repulsion increase, and
also the volume of the molecules becomes appreciable compared to the total gas volume.
So then the real gases deviate considerably from the ideal gas equation. van der Waals, by
applying the laws of mechanics to individual molecules, introduced two correction terms in the
equation of ideal gas, and his equation is given as:
𝑎
(𝑝 + 2 ) (𝑣 − 𝑏) = 𝑅𝑇
𝑣
The coefficient ‘a’ was introduced to account for the existence of mutual attraction between the
𝑎
molecules. The term 2 is called the force of cohesion. The coefficient b was introduced to account for
𝑣
the volumes of the molecules, and is known as co-volume.
Real gases conform more closely with the van der Waals equation of state than the ideal gas equation
of state, particularly at higher pressures. But it is not obeyed by a real gas in all ranges of pressures
and temperatures. Many more equations of state were later introduced, and notable among these are
the following equations
𝑅𝑇 𝑎
𝐵𝑒𝑟𝑡ℎ𝑒𝑙𝑜𝑡: 𝑝= − 2
𝑣 − 𝑏 𝑇𝑣
𝑅𝑇
𝐷𝑖𝑒𝑡𝑒𝑟𝑖𝑐𝑖: 𝑝= . 𝑒 −𝑎⁄𝑅𝑇𝑣
𝑣−𝑏
𝑅𝑇 𝑎
𝑅𝑒𝑑𝑙𝑖𝑐ℎ − 𝐾𝑤𝑜𝑛𝑔: 𝑝= − 1⁄2
𝑣 − 𝑏 𝑇 𝑣(𝑣 + 𝑏)

The constants, a and b can be evaluated from the critical data.

The Berthelot and Dieterici equations of state, like the van der Waals equation, are of limited accuracy.
But the Redlich-Kwong equation gives good results at high pressures and is fairly accurate for
temperatures above the critical value.
All these equations mentioned above reduce to the ideal gas equation for large volumes and
temperatures and for very small pressures.

VIRIAL EXPANSIONS
This is the virial equation of state, the most general function relating pressure, P, density, ρ, and
temperature, T, of fluids. It was first introduced by the Dutch physicist, Kammerlingh Onnes. The
relations between 𝑝𝑣 and 𝑝 in the form of power series may be expressed as
𝑝𝑣 = 𝑅𝑇(1 + 𝐵 ′ 𝑝 + 𝐶 ′ 𝑝2 + 𝐷′ 𝑝3 + ⋯ )
For any gas,
lim 𝑝𝑣 = 𝑅𝑇
𝑝→0
Therefore,
𝑝𝑣 𝑝𝑣
= = 1 + 𝐵 ′ 𝑝 + 𝐶 ′ 𝑝2 + 𝐷′ 𝑝3 + ⋯
𝑅𝑇 𝑅𝑇
An alternative expression is
𝑝𝑣 𝑝𝑣 𝐵 𝐶 𝐷
= =1+ + 2+ 3+⋯
𝑅𝑇 𝑅𝑇 𝑣 𝑣 𝑣
Both expressions are known as virial expansions or virial equations of state,
𝐵 ′ , 𝐶 ′ , 𝐵, 𝐶, etc. are called virial coefficients. 𝐵 ′ , 𝑎𝑛𝑑 𝐵 are called second virial coefficients, 𝐶 ′ , 𝐶,
are called third virial coefficients, and so on. For a given gas, these coefficients are functions of
temperature only.
𝑝𝑣
The ratio 𝑅𝑇 is called the compressibility factor, Z. For an ideal gas Z = 1.
At very low pressures Z approaches unity, as a real gas approaches the ideal gas behaviour. The
magnitude of Z for a certain gas at a particular pressure and temperature gives an indication of the
extent of deviation of the gas from the ideal gas behaviour. The virial expansions become
𝑍 = 1 + 𝐵 ′ 𝑝 + 𝐶 ′ 𝑝2 + 𝐷′ 𝑝3 + ⋯
And
 𝑝𝑣 𝐵 𝐶 𝐷
𝑍= =1+ + 2+ 3+⋯
𝑅𝑇 𝑣 𝑣 𝑣
𝑅𝑇 𝐵 𝐶 𝐷
𝑝 = ( ) (1 + + 2 + 3 + ⋯ )
𝑣 𝑣 𝑣 𝑣
′ ′
The relations between 𝐵 , 𝐶 , 𝑎𝑛𝑑 𝐵, 𝐶, … can be derived as given below:
𝑝𝑣
= 𝑍 = 1 + 𝐵 ′ 𝑝 + 𝐶 ′ 𝑝2 + 𝐷′ 𝑝3 + ⋯
𝑅𝑇
2 2
𝑅𝑇 𝐵 𝐶 𝐷 𝑅𝑇 𝐵 𝐶 𝐷
= 1 + 𝐵 [( ) (1 + + 2 + 3 + ⋯ )] + 𝐶 ′ [( ) (1 + + 2 + 3 + ⋯ ) ]
′
𝑣 𝑣 𝑣 𝑣 𝑣 𝑣 𝑣 𝑣
3 3
′
𝑅𝑇 𝐵 𝐶 𝐷
+ 𝐷 [( ) (1 + + 2 + 3 + ⋯ ) ] …
𝑣 𝑣 𝑣 𝑣
2 2 3
𝐵′𝑅𝑇 𝐵 ′ 𝐵𝑅𝑇 + 𝐶′(𝑅𝑇) 𝐵 ′ 𝐶𝑅𝑇 + 2𝐵𝐶 ′ (𝑅𝑇) + 𝐷′(𝑅𝑇)
=1+ + 2 + 3 +⋯
𝑣 𝑣 𝑣
Comparing with the equation
𝑝𝑣 𝐵 𝐶 𝐷
=1+ + 2+ 3+⋯
𝑅𝑇 𝑣 𝑣 𝑣
𝐵
𝐵 ′ 𝑅𝑇 = 𝐵 → 𝐵′ =
𝑅𝑇
2 2 𝐶 − 𝐵2
𝐶 = 𝐵 ′ 𝐵𝑅𝑇 + 𝐶 ′ (𝑅𝑇) = 𝐵 2 + 𝐶 ′ (𝑅𝑇) → 𝐶 ′ = 2
(𝑅𝑇)
2 3 3
𝐷 = 𝐵 ′ 𝐶𝑅𝑇 + 2𝐵𝐶 ′ (𝑅𝑇) + 𝐷′ (𝑅𝑇) = 𝐵𝐶 + 2𝐵(𝐶 − 𝐵 2 ) + 𝐷 ′ (𝑅𝑇)
′
𝐷 − 3𝐵𝐶 + 2𝐵 3
→𝐷 = 3
(𝑅𝑇)
Therefore,
𝑝𝑣 𝐵 𝐶 − 𝐵 2 2 𝐷 − 3𝐵𝐶 + 2𝐵 3 3
𝑍= = 1 + 𝐵 ′ 𝑝 + 𝐶 ′ 𝑝2 + 𝐷′ 𝑝3 + ⋯ = 1 + 𝑝+ 2 𝑝 + 3 𝑝 +⋯
𝑅𝑇 𝑅𝑇 (𝑅𝑇) (𝑅𝑇)
𝐵 𝐶 𝐷
=1+ + 2+ 3+⋯
𝑣 𝑣 𝑣
𝐵 𝐶
The terms 𝑣 , 2 , etc. of the virial expansion arise on account of molecular interactions. If no such
𝑣
interactions exist (at very low pressures) B = 0, C = 0, etc. Z = 1 and 𝑝𝑣 = 𝑅𝑇.
Van der Waals equation of state can be expressed in the virial form as given below
𝑎 𝑎 𝑏
(𝑝 + 2 ) (𝑣 − 𝑏) = 𝑅𝑇 → (𝑝𝑣 + ) (1 − ) = 𝑅𝑇
𝑣 𝑣 𝑣
−1
𝑎 𝑏 𝑏 𝑏2 𝑏3 𝑏
𝑝𝑣 + = 𝑅𝑇 (1 − ) = 𝑅𝑇 [1 + + 2 + 3 + ⋯ ] 𝑤ℎ𝑒𝑟𝑒, < 1
𝑣 𝑣 𝑣 𝑣 𝑣 𝑣
𝑎 1 𝑏2 𝑏3
𝑝𝑣 = 𝑅𝑇 [1 + (𝑏 − ) + 2 + 3 + ⋯ ]
𝑅𝑇 𝑣 𝑣 𝑣
𝐶𝑜𝑚𝑝𝑎𝑟𝑖𝑛𝑔 𝑤𝑖𝑡ℎ
𝐵 𝐶 𝐷
𝑝𝑣 = 𝑅𝑇 [1 + + 2 + 3 + ⋯ ]
𝑣 𝑣 𝑣
𝑎
The second virial coefficient 𝐵 = (𝑏 − 𝑅𝑇), the third virial coefficient 𝐶 = 𝑏 2 , etc.
COMPRESSIBILITY CHART
For a certain gas, the compressibility factor Z is a function of p and T. So a plot can be made of lines
of constant temperature on coordinates of p and Z. This is called compressibility chart.
From this plot Z can be obtained for any value of p and T, and the volume can then be obtained from
the equation pv = ZRT. The advantage of using Z instead of a direct plot of v is a smaller range of
values in plotting.

GENERALIZED COMPRESSIBILITY CHART

For each substance, there is a compressibility chart. It would be very convenient if one chart could be
used for all substances. This can be achieved by using dimensionless properties called reduced
properties.
Definition of reduced properties: The reduced pressure is the ratio of the existing pressure to the critical
pressure of the substance, and similarly for reduced temperature and reduced volume. Then,
𝑝 𝑇 𝑣
𝑝𝑟 = ; 𝑇𝑟 = ; 𝑎𝑛𝑑 𝑣𝑟 =
𝑝𝑐 𝑇𝑐 𝑣𝑐
where subscript r denotes the reduced property, and subscript c denotes the property at the critical state.

At the same pressure and temperature the specific or molal volumes of different gases are different.
However, it is found from experimental data that at the same reduced pressure and reduced
temperature, the reduced volumes of different gases are approximately the same.
Therefore, for all substances
𝑣𝑟 = 𝑓(𝑝𝑟 , 𝑇𝑟 )
Now,
𝑣 𝑍𝑅𝑇 𝑝𝑐 𝑍 𝑇𝑟
𝑣𝑟 = = × = .
𝑣𝑐 𝑝 𝑍𝑐 𝑅𝑇𝑐 𝑍𝑐 𝑝𝑟
where
𝑝𝑐 𝑣𝑐
𝑍𝑐 = 𝑖𝑠 𝑐𝑎𝑙𝑙𝑒𝑑 𝑡ℎ𝑒 𝑐𝑟𝑖𝑡𝑖𝑐𝑎𝑙 𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑖𝑏𝑖𝑙𝑖𝑡𝑦 𝑓𝑎𝑐𝑡𝑜𝑟
𝑅𝑇𝑐
Therefore, from the above two equations,
𝑍 = 𝑓(𝑝𝑟 , 𝑇𝑟 , 𝑍𝑐 )
Experimental values of 𝑍𝑐 for most substances fall within a narrow range 0.20 – 0.30. Therefore, 𝑍𝑐
may be taken to be a constant and therefore,
𝑍 ≈ 𝑓(𝑝𝑟 , 𝑇𝑟 )
When lines with constant 𝑇𝑟 is plotted on the coordinates of reduced pressure, 𝑝𝑟 and Z, a single plot,
known as the generalized compressibility chart, is found to be satisfactory for a great variety of
substances.

Significance: Although necessarily approximate, the plots are extremely useful in situations where
detailed data on a particular gas are lacking but its critical properties are available. This type of charts
in terms of reduced properties is very useful in predicting the properties of substances for which more
precise data are not available.

Use of the chart: Knowing the critical properties of a substance, at any given temperature and pressure
(p, T), its reduced temperature and pressure (𝑝𝑟 , 𝑇𝑟 ) can be estimated. Then from the chart Z and v can
be obtained.

LAW OF CORRESPONDING STATES

A functional relationship between the reduced properties, 𝒑𝒓 , 𝑻𝒓 𝒂𝒏𝒅 𝒗𝒓 , is known as the law
of corresponding states, which is independent of the nature of the substance. It can be derived from the
various equations of state, such as those of van der Waals, Berthelot, and Dieterici. For a van der Waals
gas,
𝑎
(𝑝 + 2 ) (𝑣 − 𝑏) = 𝑅𝑇
𝑣
where a, b, and R are the characteristic constants of the particular gas.
 𝑅𝑇 𝑎
𝑝= − 2 → 𝑝𝑣 2 (𝑣 − 𝑏) − 𝑅𝑇𝑣 2 + 𝑎(𝑣 − 𝑏) = 0 → 𝑝𝑣 3 − (𝑝𝑏 + 𝑅𝑇)𝑣 2 + 𝑎𝑣 − 𝑎𝑏 = 0
𝑣−𝑏 𝑣
It is therefore a cubic in v and for given values of p and T has three roots of which only one need be
real. For low temperatures, three positive real roots exist for a certain range of pressure (for example,
at triple point). As the temperature increases the three real roots approach one another and at the critical
temperature they become equal. Above this temperature only one real root exists for all values of p.

For the critical isotherm T = Tc on the p-v plane, the three real roots coincide at the critical point,
where the isotherm has a zero slope and also it is a point of inflection, since its slope changes direction.
Therefore, the first and second derivatives of p with respect to v are each equal to zero for the isotherm
T = Tc at the critical point. Therefore,
𝑅𝑇 𝑎
𝑝= − 2
𝑣−𝑏 𝑣
𝜕𝑝 𝑅𝑇𝑐 2𝑎 2𝑎 𝑅𝑇𝑐
( ) =− + 3 = 0 → 3 =
𝜕𝑣 𝑇=𝑇𝑐 (𝑣𝑐 − 𝑏)2 𝑣𝑐 𝑣𝑐 (𝑣𝑐 − 𝑏)2
𝜕2𝑝 2𝑅𝑇𝑐 6𝑎 2𝑅𝑇𝑐 3 𝑅𝑇𝑐
( 2) = 3
− 4 =0 → 3
− × =0
𝜕𝑣 𝑇=𝑇 (𝑣𝑐 − 𝑏) 𝑣𝑐 (𝑣𝑐 − 𝑏) 𝑣𝑐 (𝑣𝑐 − 𝑏)2
𝑐
2 3 𝑣𝑐
→ − =0→𝑏=
𝑣𝑐 − 𝑏 𝑣𝑐 3
Substituting in
2𝑎 𝑅𝑇𝑐
3 = (𝑣 − 𝑏)2
𝑣𝑐 𝑐
2
2
2𝑎 4𝑣 𝑐 2𝑎 8𝑎
𝑅𝑇𝑐 = (𝑣𝑐 − 𝑏) × 3 = × 3 →𝑅=
𝑣𝑐 9 𝑣𝑐 9𝑇𝑐 𝑣𝑐
Substituting the values of b and R in the van der Waals equation at the critical point,
𝑎
(𝑝𝑐 + 2 ) (𝑣𝑐 − 𝑏) = 𝑅𝑇𝑐
𝑣𝑐
𝑎 2 8𝑎
⟹ (𝑝𝑐 + 2 ) ( 𝑣𝑐 ) = × 𝑇𝑐
𝑣𝑐 3 9𝑇𝑐 𝑣𝑐

8𝑎 3 𝑎 𝑎
⟹ 𝑝𝑐 = × − 2= → 𝑎 = 3𝑝𝑐 𝑣𝑐 2
9𝑣𝑐 2𝑣𝑐 𝑣𝑐 3𝑣𝑐 2
Therefore, the value of R becomes
8 8 𝑝𝑐 𝑣𝑐
𝑅= × 3𝑝𝑐 𝑣𝑐 2 =
9𝑇𝑐 𝑣𝑐 3 𝑇𝑐
The values of a, b, and R have thus been expressed in terms of critical properties.
Substituting these in the van der Waals equation of state
𝑎
(𝑝 + 2 ) (𝑣 − 𝑏) = 𝑅𝑇
𝑣

3𝑝𝑐 𝑣𝑐 2 𝑣𝑐 8 𝑝𝑐 𝑣𝑐
(𝑝 + ) (𝑣 − ) = 𝑇
𝑣2 3 3 𝑇𝑐
𝑝 3𝑣𝑐 2 𝑣 1 8𝑇
⟹ ( + 2 )( − ) =
𝑝𝑐 𝑣 𝑣𝑐 3 3 𝑇𝑐
Using the reduced parameters,
3
(𝑝𝑟 + 2 ) (3𝑣𝑟 − 1) = 8𝑇𝑟
𝑣𝑟
In the reduced equation of state, the individual coefficients a, b and R for a particular gas have
disappeared. So this equation is an expression of the law of corresponding states because it reduces the
properties of all gases to one formula.

Two different substances are considered to be in ‘corresponding states’, if their pressures, volumes and
temperatures are of the same fractions (or multiples) of the critical pressure, volume and temperature
of the two substances. i.e.,
𝑝𝑟1 = 𝑝𝑟2 , 𝑣𝑟1 = 𝑣𝑟2 , 𝑎𝑛𝑑 𝑇𝑟1 = 𝑇𝑟2 ,
Or,
𝑝1 𝑝2 𝑣1 𝑣2 𝑇1 𝑇2
= ; = ; 𝑎𝑛𝑑 =
𝑝𝑐1 𝑝𝑐2 𝑣𝑐1 𝑣𝑐2 𝑇𝑐1 𝑇𝑐2
The value of Z at the critical state of a van der Waals gas is
8 𝑝𝑐 𝑣𝑐 𝑝𝑐 𝑣𝑐 3
𝑅= →𝑍= = = 0.375 ≪ 1
3 𝑇𝑐 𝑅𝑇𝑐 8
𝒑𝒓 𝒗𝒓 vs. 𝒑𝒓 diagram
3
(𝑝𝑟 + 2 ) (3𝑣𝑟 − 1) = 8𝑇𝑟
𝑣𝑟

The reduced equation can also be written in the following form

 3
(𝑝𝑟 + ) (3𝑣𝑟 − 1) = 8𝑇𝑟
𝑣𝑟 2
3 8𝑇𝑟 𝑣𝑟 3
(𝑝𝑟 𝑣𝑟 + ) (3𝑣𝑟 − 1) = 8𝑇𝑟 𝑣𝑟 → 𝑝𝑟 𝑣𝑟 = −
𝑣𝑟 3𝑣𝑟 − 1 𝑣𝑟
To find the minima of the isotherms in 𝑝𝑟 𝑣𝑟 vs. 𝑝𝑟 diagram,
𝜕(𝑝𝑟 𝑣𝑟 )
[ ] =0
𝜕𝑝𝑟 𝑇
𝑟

𝜕(𝑝𝑟 𝑣𝑟 ) 𝜕𝑣𝑟 𝜕(𝑝𝑟 𝑣𝑟 ) 𝜕𝑣𝑟

⇒[ ] [ ] =0⇒[ ] = 0 𝑠𝑖𝑛𝑐𝑒, [ ] ≠0
𝜕𝑣𝑟 𝑇 𝜕𝑝𝑟 𝑇 𝜕𝑣𝑟 𝑇 𝜕𝑝𝑟 𝑇
𝑟 𝑟 𝑟 𝑟

𝜕(𝑝𝑟 𝑣𝑟 ) 𝜕 8𝑇𝑟 𝑣𝑟 3
⇒[ ] = [ − ] =0
𝜕𝑣𝑟 𝑇 𝜕𝑣𝑟 3𝑣𝑟 − 1 𝑣𝑟 𝑇𝑟
𝑟

8𝑇𝑟 8𝑇𝑟 𝑣𝑟 . 3 3
⇒ − 2
+ 2=0
3𝑣𝑟 − 1 (3𝑣𝑟 − 1) 𝑣𝑟
24𝑇𝑟 𝑣𝑟 − 8𝑇𝑟 − 24𝑇𝑟 𝑣𝑟 3
⇒ 2
+ 2=0
(3𝑣𝑟 − 1) 𝑣𝑟
3(3𝑣𝑟 − 1)2 3
⇒ 2
= 8𝑇𝑟 = (𝑝𝑟 + 2 ) (3𝑣𝑟 − 1)
𝑣𝑟 𝑣𝑟
⇒ 3(3𝑣𝑟 − 1) = 𝑝𝑟 𝑣𝑟 2 + 3
⇒ 𝑝𝑟 𝑣𝑟 2 − 9𝑣𝑟 + 6 = 0
⇒ (𝑝𝑟 𝑣𝑟 )2 − 9𝑝𝑟 𝑣𝑟 + 6𝑝𝑟 = 0
𝑊ℎ𝑒𝑛 𝑝𝑟 → 0; 𝑝𝑟 𝑣𝑟 = 0 , 9

This is the equation of a parabola passing through the minima of the isotherms which intersect 𝑝𝑟 →
0 axis at 𝑝𝑟 𝑣𝑟 = 0 𝑎𝑛𝑑 9.

Again, to find the slope of the parabola,

9𝑝𝑟 𝑣𝑟 − (𝑝𝑟 𝑣𝑟 )2 𝑑𝑝𝑟 9 − 2𝑝𝑟 𝑣𝑟
𝑝𝑟 = ⇒ =
6 𝑑(𝑝𝑟 𝑣𝑟 ) 6
To find the vertex of the parabola
𝑑𝑝𝑟 9 − 2𝑝𝑟 𝑣𝑟
⇒ = = 0 ⇒ 𝑝𝑟 𝑣𝑟 = 4.5
𝑑(𝑝𝑟 𝑣𝑟 ) 6
9𝑝𝑟 𝑣𝑟 − (𝑝𝑟 𝑣𝑟 )2 9 × 4.5 − (4.5)2
𝑎𝑛𝑑, 𝑝𝑟 = = = 3.375
6 6
The parabola has the vertex at 𝑝𝑟 𝑣𝑟 = 4.5 and 𝑝𝑟 = 3.375, and it intersects the ordinate at 0 and 9.

Each isotherm with Tr < TB has a minimum. The TB isotherm has an initial horizontal portion (𝑝𝑟 𝑣𝑟 =
𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡) so that Boyle’s law is obeyed fairly accurately up to moderate pressures. Hence, the
corresponding temperature is called the Boyle temperature for that gas. Above the Boyle temperature,
the isotherms slope upward and show no minima.
As T is reduced below the critical (i.e. for 𝑇𝑟 < 1), the gas becomes liquefied, and during phase
transition isotherms are vertical. The minima of all these isotherms (𝑇𝑟 < 1) lie in the liquid zone.
Boyle’s law and Boyle Temperature
Boyle’s law states: The absolute pressure exerted by a given mass of an ideal gas is inversely
proportional to the volume it occupies if the temperature and the amount of gas remain unchanged
within a closed volume. Mathematically,
1
𝑊ℎ𝑒𝑛 𝑇 𝑎𝑛𝑑 𝑚 𝑎𝑟𝑒 𝑘𝑒𝑝𝑡 𝑢𝑛𝑐ℎ𝑎𝑛𝑔𝑒𝑑, 𝑝 ∝ → 𝑃𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑉
Boyle temperature is the temperature at which non-ideal gases behave like an ideal gas. The gas tends
to behave like an ideal gas over a wider range of pressure when the temperature reaches the Boyle
temperature. To determine Boyle temperature,
𝜕(𝑝𝑟 𝑣𝑟 ) 𝜕(𝑝𝑣)
lim [ ] = 0, → lim [ ] = 0,
𝑝𝑟 →0 𝜕𝑝𝑟 𝑇 𝑝→0 𝜕𝑝 𝑇
𝑟
For virial expansion:
′ ′ 2 ′ 3
𝐵 𝐶 − 𝐵2 2
𝐷 − 3𝐵𝐶 + 2𝐵 3
𝑝𝑣 = 𝑅𝑇[1 + 𝐵 𝑝 + 𝐶 𝑝 + 𝐷 𝑝 + ⋯ ] = 𝑅𝑇 [1 + 𝑝+ 2 𝑝 + 3 𝑝3 + ⋯ ]
𝑅𝑇 (𝑅𝑇) (𝑅𝑇)
𝜕(𝑝𝑣) 𝐵 𝐶 − 𝐵2 𝐷 − 3𝐵𝐶 + 2𝐵 3
⇒[ ] = 𝑅𝑇 [ + 2
(2𝑝) + 3
(3𝑝) + ⋯ ]
𝜕𝑝 𝑇 𝑅𝑇 (𝑅𝑇) (𝑅𝑇)
𝜕(𝑝𝑣) 𝐵
⇒ lim [ ] = = 0, ⇒ 𝐵 = 0
𝑝→0 𝜕𝑝 𝑇 𝑅𝑇

Therefore, Boyle temperature is obtained at the temperature for which the second virial coefficient is
zero. Therefore, the second virial coefficient is the most important. When B is known, the behaviour
of the gas at moderate pressures is completely determined. The terms which contain higher power
𝐶 𝐷
( 2, , 𝑒𝑡𝑐. ) becomes significant only at very high pressures.
𝑣 𝑣3
Van der Waals equation of state can be expressed in the virial form as given below
𝑎 𝑎 𝑏
(𝑝 + 2 ) (𝑣 − 𝑏) = 𝑅𝑇 → (𝑝𝑣 + ) (1 − ) = 𝑅𝑇
𝑣 𝑣 𝑣
−1
𝑎 𝑏 𝑏 𝑏2 𝑏3 𝑏
𝑝𝑣 + = 𝑅𝑇 (1 − ) = 𝑅𝑇 [1 + + 2 + 3 + ⋯ ] 𝑤ℎ𝑒𝑟𝑒, < 1
𝑣 𝑣 𝑣 𝑣 𝑣 𝑣
2 3
𝑎 1 𝑏 𝑏
𝑝𝑣 = 𝑅𝑇 [1 + (𝑏 − ) + 2 + 3 + ⋯ ]
𝑅𝑇 𝑣 𝑣 𝑣
𝐶𝑜𝑚𝑝𝑎𝑟𝑖𝑛𝑔 𝑤𝑖𝑡ℎ
𝐵 𝐶 𝐷
𝑝𝑣 = 𝑅𝑇 [1 + + 2 + 3 + ⋯ ]
𝑣 𝑣 𝑣
𝑎
The second virial coefficient 𝐵 = (𝑏 − ), the third virial coefficient 𝐶 = 𝑏 2 , etc.
𝑅𝑇
At Boyle temperature,
𝑎 𝑎
𝐵 = (𝑏 − ) = 0 ⇒ 𝑇𝐵 =
𝑅𝑇𝐵 𝑏𝑅
𝑣𝑐 8 𝑝𝑐 𝑣𝑐
𝑆𝑖𝑛𝑐𝑒, 𝑏 = ; 𝑎 = 3𝑝𝑐 𝑣𝑐 2 𝑎𝑛𝑑 𝑅 =
3 3 𝑇𝑐
𝑎 3 3𝑇𝑐 27𝑇𝑐 𝑇𝐵
𝑇𝐵 = = 3𝑝𝑐 𝑣𝑐 2 × × = ⇒ = 3.375
𝑏𝑅 𝑣𝑐 8𝑝𝑐 𝑣𝑐 8 𝑇𝑐
Maximum Inversion temperature
𝜕𝑇 1 𝜕𝑣
𝜇𝐽 = ( ) = [𝑇 ( ) − 𝑣]
𝜕𝑝 ℎ 𝑐𝑝 𝜕𝑇 𝑝
The condition for maximum inversion temperature is,
lim 𝜇𝐽 = 0
𝑝→0
From virial expansion:
𝑝𝑣 = 𝑅𝑇[1 + 𝐵 ′ 𝑝 + 𝐶 ′ 𝑝2 + 𝐷′ 𝑝3 + ⋯ ]
𝑅𝑇
⟹𝑣= + 𝑅𝑇𝐵 ′ + 𝑅𝑇𝐶 ′ 𝑝 + 𝑅𝑇𝐷′ 𝑝2 + ⋯
𝑝
𝜕𝑣 𝑅 ′
𝑑𝐵 ′ 𝑑𝐶′
⟹ ( ) = + 𝑅𝐵 + 𝑅𝑇 + 𝑅𝐶 ′ 𝑝 + 𝑅𝑇𝑝 +⋯
𝜕𝑇 𝑝 𝑝 𝑑𝑇 𝑑𝑇

𝜕𝑣
⟹ 𝑇( ) −𝑣
𝜕𝑇 𝑝
𝑅𝑇 ′ 2
𝑑𝐵 ′ ′ 2
𝑑𝐶 ′
= [ + 𝑅𝑇𝐵 + 𝑅𝑇 + 𝑅𝑇𝐶 𝑝 + 𝑅𝑇 𝑝 +⋯]
𝑝 𝑑𝑇 𝑑𝑇
𝑅𝑇 𝑑𝐵 ′ 𝑑𝐶 ′
− [ + 𝑅𝑇𝐵 ′ + 𝑅𝑇𝐶 ′ 𝑝 + 𝑅𝑇𝐷′ 𝑝2 + ⋯ ] = 𝑅𝑇 2 + 𝑅𝑇 2 𝑝 +⋯
𝑝 𝑑𝑇 𝑑𝑇
𝜕𝑣 𝑑𝐵′
⟹ lim [𝑇 ( ) − 𝑣] = 𝑅𝑇 2
𝑝→0 𝜕𝑇 𝑝 𝑑𝑇
Therefore,
1 𝜕𝑣 𝑅𝑇 2 𝑑𝐵′
lim 𝜇𝐽 = lim [𝑇 ( ) − 𝑣] =
𝑝→0 𝑝→0 𝑐𝑝 𝜕𝑇 𝑝 𝑐𝑝 𝑑𝑇
The necessary condition for maximum inversion temperature,
𝑅𝑇 2 𝑑𝐵′ 𝑑𝐵′
lim 𝜇𝐽 = =0⇒ =0
𝑝→0 𝑐𝑝 𝑑𝑇 𝑑𝑇
For van der Waals gas,
𝑎 𝐵 𝑏 𝑎
𝐵 = (𝑏 − ) 𝑎𝑛𝑑 𝐵 ′ = = −
𝑅𝑇 𝑅𝑇 𝑅𝑇 (𝑅𝑇)2

𝑑𝐵′ 𝑑 𝑏 𝑎 𝑏 2𝑎
= ( − 2
)=− 2+ 2 3
𝑑𝑇 𝑑𝑇 𝑅𝑇 (𝑅𝑇) 𝑅𝑇 𝑅 𝑇
Thus, for maximum inversion temperature, (𝑇𝑖 ),
𝑑𝐵′ 𝑏 2𝑎 2𝑎
=0 →− + = 0 ⇒ 𝑇𝑖 =
𝑑𝑇 𝑅𝑇𝑖 2 𝑅 2 𝑇𝑖 3 𝑏𝑅
Since, for van der Waals gas,
𝑣𝑐 8 𝑝𝑐 𝑣𝑐
𝑎 = 3𝑝𝑐 𝑣𝑐 2 , 𝑏 = , 𝑎𝑛𝑑 𝑅 =
3 3 𝑇𝑐
Therefore, for van der Waals gas,
2𝑎 2 × 3𝑝𝑐 𝑣𝑐 2 54
𝑇𝑖 = = = 𝑇 = 6.75𝑇𝑐
𝑏𝑅 𝑣𝑐 × 8 𝑝𝑐 𝑣𝑐 8 𝑐
3 3 𝑇𝑐

PROPERTIES OF MIXTURES OF GASES – DALTON’S LAW OF PARTIAL PRESSURES

Let us consider a homogeneous mixture of inert ideal gases at temperature T, pressure p, and volume
V. Let us suppose there are n1 moles of gas A1, n2 moles of gas A2, ... and upto nc moles of gas Ac.
Since there is no chemical reaction, the mixture is in a state of equilibrium with the equation of state

𝑝𝑉 = (𝑛1 + 𝑛2 + ⋯ + 𝑛𝑐 )𝑅𝑇; 𝑤ℎ𝑒𝑟𝑒, 𝑅 = 8.3143 𝑘𝐽/𝑘𝑚𝑜𝑙. 𝐾

𝑛1 𝑅𝑇 𝑛2 𝑅𝑇 𝑛𝑐 𝑅𝑇
→𝑝= + +⋯+
𝑉 𝑉 𝑉
𝑛𝑘 𝑅𝑇
The expression represents the pressure that the k-th gas would exert if it occupied the volume V
𝑉
alone at temperature T. This is called the partial pressure of the kth gas and is denoted by pk. Thus,
𝑛1 𝑅𝑇 𝑛2 𝑅𝑇 𝑛𝑐 𝑅𝑇
𝑝1 = , 𝑝2 = , … 𝑝𝑐 =
𝑉 𝑉 𝑉
And,
𝑝 = 𝑝1 + 𝑝2 + … + 𝑝𝑐

This is known as Dalton’s law of partial pressures which states that the total pressure of a mixture of
ideal gases is equal to the sum of the partial pressures. Now,
𝑅𝑇 𝑅𝑇
𝑉 = (𝑛1 + 𝑛2 + ⋯ + 𝑛𝑐 ) = ∑ 𝑛𝑘 .
𝑝 𝑝
and the partial pressure of the k-th gas is
𝑛𝑘 𝑅𝑇
𝑝𝑘 =
𝑉
Substituting the value of V
𝑛𝑘 𝑅𝑇 𝑛𝑘
𝑝𝑘 = = 𝑝 = 𝑥𝑘 𝑝
𝑅𝑇 ∑ 𝑛𝑘
∑ 𝑛𝑘 .
𝑝
𝑤ℎ𝑒𝑟𝑒, ∑ 𝑛𝑘 = 𝑛1 + 𝑛2 + ⋯ + 𝑛𝑐 = 𝑇𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑔𝑎𝑠 𝑚𝑖𝑥𝑡𝑢𝑟𝑒
 𝑛
The ratio ∑ 𝑛𝑘 is called the mole fraction of the k-th gas, and is denoted by 𝑥𝑘 .
𝑘
Thus,
𝑛𝑘
𝑥𝑘 = 𝑎𝑛𝑑 ∑ 𝑥𝑘 = 1
∑ 𝑛𝑘
Again, in terms of masses
𝑝𝑘 𝑉 = 𝑚𝑘 𝑅𝑘 𝑇
→ 𝑝𝑉 = 1 + 𝑝2 + … + 𝑝𝑐 )𝑉 = (𝑚1 𝑅1 + 𝑚2 𝑅2 + ⋯ + 𝑚𝑐 𝑅𝑐 )𝑇
(𝑝
For the mixture,
𝑝𝑉 = (𝑚1 + 𝑚2 + … + 𝑚𝑐 )𝑅𝑒𝑞 𝑇
Where, 𝑅𝑒𝑞 is the gas constant for the mixture, given by,
𝑚1 𝑅1 + 𝑚2 𝑅2 + ⋯ + 𝑚𝑐 𝑅𝑐 ∑ 𝑚𝑘 𝑅𝑘
𝑅𝑒𝑞 = =
𝑚1 + 𝑚2 + … + 𝑚𝑐 ∑ 𝑚𝑘

The equivalent gas constant of the mixture is thus the weighted mean, on a mass basis, of the gas
constants of the components.

If 𝑀𝑒𝑞 is the equivalent molecular weight of the mixture and ∑ 𝑛𝑘 is the total number of moles, then
total mass of the mixture,
∑ 𝑚𝑘 = 𝑚1 + 𝑚2 + … + 𝑚𝑐

→ ∑ 𝑛𝑘 × 𝑀𝑒𝑞 = 𝑛1 𝑀1 + 𝑛2 𝑀2 + ⋯ + 𝑛𝑐 𝑀𝑐 = ∑(𝑛𝑘 𝑀𝑘 )

∑(𝑛𝑘 𝑀𝑘 )
→ 𝑀𝑒𝑞 = = 𝑥1 𝑀1 + 𝑥2 𝑀2 + ⋯ + 𝑥𝑐 𝑀𝑐 = ∑(𝑥𝑘 𝑀𝑘 )
∑ 𝑛𝑘
Therefore,
∑ 𝑚𝑘 𝑅𝑘 ∑ 𝑛𝑘 × 𝑅 𝑅
𝑅𝑒𝑞 = = =
∑ 𝑚𝑘 ∑(𝑛𝑘 𝑀𝑘 ) 𝑀𝑒𝑞

A quantity called the partial volume of a component of a mixture is the volume that the component
alone would occupy at the pressure and temperature of the mixture.
Designating the partial volumes by V1, V2, etc. then
𝑝𝑉1 = 𝑚1 𝑅1 𝑇, 𝑝𝑉2 = 𝑚2 𝑅2 𝑇, . . . . . 𝑝𝑉𝑐 = 𝑚𝑐 𝑅𝑐 𝑇,

𝑝(𝑉1 + 𝑉2 + … + 𝑉𝑐 ) = (𝑚1 𝑅1 + 𝑚2 𝑅2 + ⋯ + 𝑚𝑐 𝑅𝑐 )𝑇 = ∑(𝑚𝑘 𝑅𝑘 ) 𝑇

Since,
𝑝𝑉 = ∑ 𝑚𝑘 × 𝑅𝑒𝑞 𝑇 = ∑(𝑚𝑘 𝑅𝑘 ) 𝑇
Therefore,
𝑉 = 𝑉1 + 𝑉2 + … + 𝑉𝑐
The total volume is thus equal to the sum of the partial volumes.

The specific volume of the mixture, v, is given by

𝑉 𝑉
𝑣= =
∑ 𝑚𝑘 𝑚1 + 𝑚2 + … + 𝑚𝑐
 1 𝑚1 + 𝑚2 + … + 𝑚𝑐 𝑚1 𝑚2 𝑚𝑐 1 1 1
= = + +⋯+ = + + ⋯+
𝑣 𝑉 𝑉 𝑉 𝑉 𝑣1 𝑣2 𝑣𝑐
→ 𝜌 = 𝜌1 + 𝜌2 + ⋯ + 𝜌𝑐
where 𝑣1 , 𝑣2 , … denote specific volumes of the components, each component occupying the total
volume;  in the density of the mixture and 1, 2, … denote density of the components.

INTERNAL ENERGY, ENTHALPY AND SPECIFIC HEATS OF GAS MIXTURES

When gases at equal pressures and temperatures are mixed adiabatically without work, as by inter-
diffusion in a constant volume container, the first law requires that the internal energy of the gaseous
system remains constant,
Hence the internal energy of a mixture of gases is equal to the sum of the internal energies of the
individual components, each taken at the temperature and volume of the mixture (i.e. sum of the
‘partial’ internal energies). This is also true for any of the thermodynamic properties like H, cv, cp, S,
F, and G, and is known as Gibbs theorem. Therefore, on a mass basis

𝑚1 𝑢1 + 𝑚2 𝑢2 + ⋯ + 𝑚𝑐 𝑢𝑐
𝑚𝑢𝑚 = 𝑚1 𝑢1 + 𝑚2 𝑢2 + ⋯ + 𝑚𝑐 𝑢𝑐 → 𝑢𝑚 =
𝑚1 + 𝑚2 + … + 𝑚𝑐
𝑢𝑚 is the average specific internal energy of the mixture.

Similarly, the total enthalpy of a gas mixture is the sum of the ‘partial’ enthalpies
𝑚1 ℎ1 + 𝑚2 ℎ2 + ⋯ + 𝑚𝑐 ℎ𝑐
𝑚ℎ𝑚 = 𝑚1 ℎ1 + 𝑚2 ℎ2 + ⋯ + 𝑚𝑐 ℎ𝑐 → ℎ𝑚 =
𝑚1 + 𝑚2 + … + 𝑚𝑐
ℎ𝑚 is the average specific enthalpy of the mixture.

From the definitions of specific heats, it follows that

𝑚1 𝑐𝑣1 + 𝑚2 𝑐𝑣2 + ⋯ + 𝑚𝑐 𝑐𝑣𝑐
𝑐𝑣𝑚 =
𝑚1 + 𝑚2 + … + 𝑚𝑐
And
𝑚1 𝑐𝑝1 + 𝑚2 𝑐𝑝2 + ⋯ + 𝑚𝑐 𝑐𝑝𝑐
𝑐𝑝𝑚 =
𝑚1 + 𝑚2 + … + 𝑚𝑐

ENTROPY OF GAS MIXTURES

Gibbs theorem states that the total entropy of a mixture of gases is the sum of the partial entropies. The
partial entropy of one of the gases of a mixture is the entropy that the gas would have if it occupied the
whole volume alone at the same temperature. Let us imagine a number of inert ideal gases separated
from one another by suitable partitions, all the gases being at the same temperature T and pressure p.
The total entropy (initial)
𝑆𝑖 = 𝑛1 𝑠1 + 𝑛2 𝑠2 + ⋯ + 𝑛𝑐 𝑠𝑐 = ∑ 𝑛𝑘 𝑠𝑘
From property relation
𝑇𝑑𝑠 = 𝑑ℎ − 𝑣𝑑𝑝 = 𝑐𝑝 𝑑𝑇 − 𝑣𝑑𝑝

𝑑𝑇 𝑑𝑝
𝑑𝑠 = 𝑐𝑝 − 𝑅
𝑇 𝑝
The entropy of 1 mole of the k-th gas at T and p
 𝑑𝑇
𝑠𝑘 = ∫ 𝑐𝑝𝑘 − 𝑅𝑙𝑛𝑝 + 𝑠0𝑘 𝑤ℎ𝑒𝑟𝑒, 𝑠0𝑘 𝑖𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑜𝑓 𝑖𝑛𝑡𝑒𝑔𝑟𝑎𝑡𝑖𝑜𝑛
𝑇
Therefore,
1 𝑑𝑇 𝑠0𝑘
𝑆𝑖 = ∑ 𝑛𝑘 𝑠𝑘 = 𝑅 ∑ 𝑛𝑘 ( ∫ 𝑐𝑝𝑘 + − 𝑙𝑛𝑝)
𝑅 𝑇 𝑅
Let,
1 𝑑𝑇 𝑠0𝑘
𝜎𝑘 = ∫ 𝑐𝑝𝑘 +
𝑅 𝑇 𝑅
Then
𝑆𝑖 = 𝑅 ∑ 𝑛𝑘 (𝜎𝑘 − 𝑙𝑛𝑝)
After the partitions are removed, the gases diffuse into one another at the same temperature and
pressure, and by Gibbs theorem, the entropy of the mixture, 𝑆𝑓 , is the sum of the partial entropies, with
each gas exerting its respective partial pressure. Thus,

𝑆𝑓 = 𝑅 ∑ 𝑛𝑘 (𝜎𝑘 − 𝑙𝑛𝑝𝑘 ) = 𝑅 ∑ 𝑛𝑘 (𝜎𝑘 − 𝑙𝑛𝑝 − 𝑙𝑛𝑥𝑘 ) 𝑠𝑖𝑛𝑐𝑒, 𝑝𝑘 = 𝑥𝑘 𝑝

A change in entropy due to the diffusion of any number of inert ideal gases is
𝑆𝑓 − 𝑆𝑖 = −𝑅 ∑ 𝑛𝑘 𝑙𝑛𝑥𝑘 = −𝑅(𝑛1 𝑙𝑛𝑥1 + 𝑛2 𝑙𝑛𝑥2 + ⋯ + 𝑛𝑐 𝑙𝑛𝑥𝑐 )
Since the mole fractions are less than unity, (𝑆𝑓 − 𝑆𝑖 ) is always positive, conforming to the Second
Law. Again
𝑝1 𝑝2 𝑝𝑐
𝑆𝑓 − 𝑆𝑖 = −𝑅 (𝑛1 𝑙𝑛 ( ) + 𝑛2 𝑙𝑛 ( ) + ⋯ + 𝑛𝑐 𝑙𝑛 ( ))
𝑝 𝑝 𝑝
which indicates that each gas undergoes in the diffusion process a free expansion from total pressure
p to the respective partial pressure at constant temperature.

Similarly, on a mass basis, the entropy change due to diffusion

𝑝𝑘
𝑆𝑓 − 𝑆𝑖 = − ∑ 𝑚𝑘 𝑅𝑘 𝑙𝑛 ( )
𝑝
𝑝1 𝑝2 𝑝𝑐
= − [𝑚1 𝑅1 𝑙𝑛 ( ) + 𝑚2 𝑅2 𝑙𝑛 ( ) + ⋯ + 𝑚𝑐 𝑅𝑐 𝑙𝑛 ( )]
𝑝 𝑝 𝑝

GIBBS FUNCTION OF A MIXTURE OF INERT IDEAL GASES

From the equations
𝑑𝑇 𝑑𝑝
𝑑ℎ = 𝑐𝑝 𝑑𝑇 𝑎𝑛𝑑 𝑑𝑠 = 𝑐𝑝 − 𝑅
𝑇 𝑝
the enthalpy and entropy of 1 mole of an ideal gas at temperature T and pressure p are
ℎ = ℎ0 + ∫ 𝑐𝑝 𝑑𝑇
𝑑𝑇
𝑠 = 𝑠0 + ∫ 𝑐𝑝 − 𝑅𝑙𝑛𝑝
𝑇
Therefore, the molar Gibbs function
𝑑𝑇
𝑔 = ℎ − 𝑇𝑠 = ℎ0 + ∫ 𝑐𝑝 𝑑𝑇 − 𝑇𝑠0 − 𝑇 ∫ 𝑐𝑝 + 𝑅𝑇𝑙𝑛𝑝
𝑇
Since,
∫ 𝑑(𝑢𝑣) = ∫ 𝑢𝑑𝑣 + ∫ 𝑣𝑑𝑢 = 𝑢𝑣
Let,
1
𝑢= , 𝑎𝑛𝑑 𝑣 = ∫ 𝑐𝑝 𝑑𝑇
𝑇
Then,
1
𝑑𝑢 = − 𝑑𝑇, 𝑎𝑛𝑑 𝑑𝑣 = 𝑐𝑝 𝑑𝑇
𝑇2

1 1 1
∫ 𝑐𝑝 𝑑𝑇 = ∫ 𝑐𝑝 𝑑𝑇 + ∫ (∫ 𝑐𝑝 𝑑𝑇) (− 2 ) 𝑑𝑇
𝑇 𝑇 𝑇

𝑑𝑇 (∫ 𝑐𝑝 𝑑𝑇)
→ ∫ 𝑐𝑝 𝑑𝑇 − 𝑇 ∫ 𝑐𝑝 = −𝑇 ∫ 𝑑𝑇
𝑇 𝑇2
Therefore,
𝑑𝑇
𝑔 = ℎ0 + ∫ 𝑐𝑝 𝑑𝑇 − 𝑇𝑠0 − 𝑇 ∫ 𝑐𝑝 + 𝑅𝑇𝑙𝑛𝑝
𝑇
(∫ 𝑐𝑝 𝑑𝑇)
= ℎ0 − 𝑇 ∫ 𝑑𝑇 − 𝑇𝑠0 + 𝑅𝑇𝑙𝑛𝑝
𝑇2
ℎ0 1 (∫ 𝑐𝑝 𝑑𝑇) 𝑠0
= 𝑅𝑇 ( − ∫ 𝑑𝑇 − + 𝑙𝑛𝑝)
𝑅𝑇 𝑅 𝑇2 𝑅
Let,
ℎ0 1 (∫ 𝑐𝑝 𝑑𝑇) 𝑠0
𝜙= − ∫ 𝑑𝑇 −
𝑅𝑇 𝑅 𝑇2 𝑅
Thus,
𝑔 = 𝑅𝑇(𝜙 + 𝑙𝑛𝑝)
where  is a function of temperature only.

Let us consider a number of inert ideal gases separated from one another at the same T and p. Initial
Gibbs function is:
𝐺𝑖 = ∑ 𝑛𝑘 𝑔𝑘 = 𝑅𝑇 ∑ 𝑛𝑘 (𝜙 + 𝑙𝑛𝑝)

After the partitions are removed, the gases will diffuse, and the partial Gibbs function of a particular
gas is the value of G, if that gas occupies the same volume at the same temperature exerting a partial
pressure pK. Thus, final Gibbs function is,

𝐺𝑓 = 𝑅𝑇 ∑ 𝑛𝑘 (𝜙𝑘 + 𝑙𝑛𝑝𝑘 ) = 𝑅𝑇 ∑ 𝑛𝑘 (𝜙𝑘 + 𝑙𝑛𝑝 + 𝑙𝑛𝑥𝑘 ) 𝑠𝑖𝑛𝑐𝑒, 𝑝𝑘 = 𝑥𝑘 𝑝

Therefore,
𝐺𝑓 − 𝐺𝑖 = 𝑅𝑇 ∑ 𝑛𝑘 𝑙𝑛𝑥𝑘
Since 𝑥𝑘 < 1, (𝐺𝑓 − 𝐺𝑖 ) is negative because G decreases due to diffusion. Gibbs function of a mixture
of ideal gases at T and p is thus
𝐺 = 𝑅𝑇 ∑ 𝑛𝑘 (𝜙𝑘 + 𝑙𝑛𝑝 + 𝑙𝑛𝑥𝑘 )